Effects of small amount of Ca doping in La site in LaCoO3-based oxide on the synthesis and electrical conductivity were investigated by using X-ray diffraction (XRD), differential scanning calorimetry and thermogravimetry (DSC/TG), ordinary four-probe dc measurement methods. La0.8Sr0.2-xCaxCo0.9Fe0.1O3-δ (LSCCF, 0≤x≤0.1) prepared by solid reaction synthesis is all of a single phase and the calcined process may be divided into three stages: (1) decomposition of reactants; (2) formation of LaCoO3-based oxides; and (3) formation of LSCCF solid solution. The maximum of electrical conductivity of the LSCCF composites is above 100 S*cm-1 and the conduction mechanism is attributed to the adiabatic-hopping of p-type small polarons.